Single crystalline NaUO3 and method of making same

ABSTRACT

The present invention relates to single crystalline NaUO3, hydrothermal growth processes of making such single crystals and methods of using such single crystals. In particular, Applicants disclose single crystalline NaUO3 in the R32 space group. Unlike other powdered NaUO3, Applicants&#39; single crystalline NaUO3 has a sufficient crystal size to be characterized and used in the fields of laser light, infrared countermeasures, nuclear fuel material, nuclear forensics and magnetic applications.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims priority to U.S. Provisional ApplicationSer. No. 62/863,981 filed Jun. 20, 2019, the contents of which is herebyincorporated by reference in their entry.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or forthe Government of the United States for all governmental purposeswithout the payment of any royalty.

FIELD OF THE INVENTION

The present invention relates to single crystalline NaUO₃, hydrothermalgrowth processes of making such single crystals and methods of usingsuch single crystals.

BACKGROUND OF THE INVENTION

Currently NaUO₃ is produced in an orthorhombic powder form, rather thansingle crystalline rhombohedral R32. Furthermore, the sole report ofrhombohedral NaUO₃ does not disclose single crystalline rhombohedral R32as the specific rhombohedral space group is not provided and there aremany different possible space groups in the rhombohedral crystal class,and such report concludes that the data obtained from synthesizedcrystal agrees with the orthorhombic data. Unfortunately, the powderedforms of NaUO₃ do not contain single crystalline NaUO₃ having asufficient crystal size for applications in the desired fields offrequency conversion of laser light, infrared countermeasures, nuclearfuel material, nuclear forensics and magnetic applications. In fact,powdered forms of NaUO₃ are made of particles that are too small toperform optical, magnetic, electrical, and physical propertycharacterizations of such material. Thus any applications that requirebulk or even thin film single crystals NaUO₃ cannot be realized withcurrent forms of NaUO₃.

Applicants recognized that the problem that impeded obtaining suitablysized single crystalline rhombohedral R32 NaUO₃ was that past processesheat a powdered mixture which impeded crystal formation. As a result,Applicants developed a process of growing NaUO₃ crystals using asupercritical temperature regime during a hydrothermal process. As aresult, Applicants were are able to increase the solubility of thefeedstock to elicit larger spontaneous nucleation and provide conditionsfor bulk crystal growth via transport growth reactions. In addition tothe aforementioned water temperature, Applicants utilized sealed silverand platinum growth ampules to avoid impurities caused by the walls ofthe autoclave or from the ampules themselves. Advantages of Applicantsprocess include ability to produce bulk NaUO₃ crystals greater than 370microns and the ability to synthesis single crystals.

As a result of the aforementioned process innovation, Applicantsdisclose single crystalline NaUO₃ that can be characterized and thathave a sufficient crystal size for use in the fields of frequencyconversion of laser light, infrared countermeasures, nuclear fuelmaterial, nuclear forensics and magnetic applications.

SUMMARY OF THE INVENTION

The present invention relates to single crystalline NaUO₃, hydrothermalgrowth processes of making such single crystals and methods of usingsuch single crystals. In particular, Applicants disclose singlecrystalline NaUO₃ in the R32 space group. Unlike other powdered NaUO₃,Applicants' single crystalline NaUO₃ has a sufficient crystal size to becharacterized and used in the fields of frequency conversion of laserlight, infrared countermeasures, nuclear fuel material, nuclearforensics and magnetic applications.

Additional objects, advantages, and novel features of the invention willbe set forth in part in the description which follows, and in part willbecome apparent to those skilled in the art upon examination of thefollowing or may be learned by practice of the invention. The objectsand advantages of the invention may be realized and attained by means ofthe instrumentalities and combinations particularly pointed out in theappended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate embodiments of the presentinvention and, together with a general description of the inventiongiven above, and the detailed description of the embodiments givenbelow, serve to explain the principles of the present invention.

FIG. 1 is a flowchart illustrating a method of synthesizinguranium-based crystals in accordance with an embodiment of the presentinvention.

FIG. 2A is a side elevational view of an autoclave, shown incross-section, suitable for performing the method of FIG. 1 according toembodiments of the present invention.

FIG. 2B is a side elevational view of an autoclave, shown incross-section, suitable for performing the method of FIG. 1 according toembodiments of the present invention.

FIG. 3 is a side elevational view of a seed rack ladder suitable for usein synthesizing uranium oxide crystals in accordance with someembodiments of the present invention.

FIG. 4 is a flowchart illustrating a method of synthesizinguranium-based seed crystals in accordance with another embodiment of thepresent invention.

FIG. 5 is a side elevational view of an autoclave, shown incross-section, suitable for performing the method of FIG. 4 according toembodiments of the present invention.

FIG. 6 is a side elevational view of an exemplary ampoule suitable foruse in synthesizing uranium oxide crystals in accordance with someembodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Unless specifically stated otherwise, as used herein, the terms “a”,“an” and “the” mean “at least one”.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

Unless otherwise noted, the written notation of the unit cell and atomiccoordinates is designed via a number and an optional second number nextto the first number in parenthesis, for example, 7.9400(16). This isunderstood by those in the art to have a value of 7.9400 plus or minus0.0016.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

DETAILED DESCRIPTION OF THE INVENTION

Single Crystalline NaUO₃

Applicants disclose a single crystalline NaUO₃ having a R32 space group.The R32 space group maybe non-centrosymmetric.

Applicants disclose the single crystalline NaUO₃ of Paragraph 0023 saidcrystal having a crystal volume of at least 1.31×10⁻³ cubic millimeters,alternatively said crystal volume being from 1.31×10⁻³ cubic millimetersto 28,372,625 cubic millimeters or alternatively said crystal volumebeing from 1.31×10⁻³ cubic millimeters to 3,511,808 cubic millimeters.

Applicants disclose the single crystalline NaUO₃ of Paragraphs 0023through 0024, said single crystalline NaUO₃ having the followingcoordinates: a cell length a of 5.8700(8)Ã-; a cell length b of5.8700(8)Ã-; and a cell length c of 7.1180(14)Ã-.

Applicants disclose the single crystalline NaUO₃ of Paragraphs 0023through 0025, said single crystalline NaUO₃ having the following,coordinates: a U1 having x=0.0000, y=0.0000 and z=−0.0000; a O1 havingx=0.231(14), y=0.3333 and z=0.21(5); and a Na1 having x=0.6667, y=0.3333and z=2.031(4).

Process of Making Single Crystalline NaUO₃

Applicants disclose a process making a single crystalline NaUO₃ having aR32 symmetry structure wherein said R32 space group maybenon-centrosymmetric, said process comprising autoclaving for a period offrom about 24 hours to about one year, preferably from about 14 days toabout 180 days, more preferably from about 90 days to about 120 days, ata pressure of from about 200 psi to about 100,000 psi, preferably fromabout 10,000 psi to about 40,000 psi, more preferably from about 20,000psi to about 25,000 psi, a container comprising an ampoule having abottom feedstock zone and a top crystal growth zone, said bottomfeedstock zone having a temperature range of from about 200° C. to 1000°C., preferably from about 300° C. to about 700° C., more preferably fromabout 350° C. to 450° C. and top crystal growth zone having atemperature range of from about 50° C. to 950° C., preferably from about200° C. to about 600° C., more preferably from about 300° C. to 400° C.,said process having a temperature gradient between said bottom feedstockzone and said top crystal growth zone of from about 1° C. to 130° C.,preferably from about 25° C. to about 80° C., more preferably from about40° C. to 60° C. and most preferably about 50° C.; said containercomprising: 0.001-4.999:5 internal fill to ampoule volume, 0.01-8:4 feedstock to mineralizer, from 0.01:4 to 4:0.01 of each powdered feed stock;preferably: 2-4.5:5 internal fill to ampoule volume, 0.5-3:4 feed stockto mineralizer, from 1:4 to 4:1 of each powdered feed stock, morepreferably 4:5 internal fill to ampoule volume, 1:4 feed stock tomineralizer, 1:1 of each powdered feed stock.

Applicants disclose the process of Paragraph 0027 wherein said crystalgrowth zone of said container comprises a seed crystal, preferably saidseed crystal has a Pm-3m space group.

Applicants disclose the process of Paragraph 0028 wherein said seedcrystal has: a cell length a of 5.8700(8); a cell length b of 5.8700(8);a cell length c of 7.1180(14); a cell angle alpha of 90.00; a cellmangle beta of 90.00; and a cell angle gamma of 120.00.

Applicants disclose the process of Paragraph 0028 wherein said seedcrystal has: a U1 having x=0.0000, y=0.0000 and z=−0.0000; a O1 havingx=0.231(14), y=0.3333 and z=0.21(5); and a Na1 having x=0.6667, y=0.3333and z=2.031(4).

Referring now to the figures, and in particular to FIG. 1, a flowchartillustrating a method 50 of synthesizing single crystals according to anembodiment of the present invention is described. In Block 52, a chamber54 within a pressurizable reaction device 56 (FIG. 2B) is prepared witha feedstock and a mineralizer solution (collectively illustrated assolution 57 in FIG. 2A).

Composition of the feedstock and the mineralizer solution depend, inpart, of the desired crystal yielded. The feedstock may be powdered orpolycrystalline and provide nutrient for crystal growth. For NaUO₃crystals, triuranium octoxide (U₃O₈), NaUO₃ or uranium trioxide (UO₃)may be used. The mineralizer solution, generally used for dissolution ofnutrient, formation of spuriously nucleated single crystals, or both,may be generally comprised of a sodium hydroxide, sodium halides, sodiumcarbonate, and mixtures thereof. Mineralizer solutions haveconcentrations ranging from about 0.1 M to about 30 M.

TABLE 1 SEED CRYSTAL (if MINERALIZER CRYSTAL any) FEEDSTOCK SOLUTIONNaUO₃ NaUO₃, UO₃, U₃O₈, and Sodium hydroxide MgTiO₃, BaTiO₃, NaUO₃Sodium halides and other sodium carbonate perovskite structure

The exemplary pressurizable reaction device 56 illustrated in FIG. 2B isan autoclave; however, those skilled in the art having the benefit ofthe disclosure provided herein would readily appreciate that theillustrated structure is non-limiting. The autoclave 56 includes a wall58 enclosing the chamber 54, which may be separated into upper and lowerregions 54 a, 54 b by a baffle 60. The baffle 60 may be constructed fromany inert material, for example, a precious metal, and includes anopening 62 therein having a diameter, d₁, selected to permit fluidcommunication there through ranging from about 15% to about 45%. In thisway, the baffle 60 permits fluidic communication between the upper andlower regions 54 a, 54 b of the chamber 54 while maintaining theseregions 54 a, 54 b as separate. Although the baffle 60 is illustrated ashaving a single opening 62, it would be readily understood that morethan one opening may be used. In-fact, according to some embodiments ofthe present invention, the baffle 60 may be porous or comprise a meshmaterial, for example.

The chamber 54 is accessible through an open end 64, into which a plug66 and seal 68 may be inserted before pressurizing the chamber 54 andsecured with a locking collar.

Externally, heaters 72, 74 (two are shown) at least partially surroundthe wall 58 of the autoclave 56, each corresponding to a respective oneof the upper and lower chambers 54 a, 54 b. The heaters 72, 74 areoperably coupled to a controller 76, which may be configured to operablycontrol the heaters 72, 74 such that the upper chamber 54 a may beheated to a temperature that is different from a temperature of thelower chamber 54 b. Said another way, the heaters 72, 74 may be operatedso as to form a temperature gradient between the upper and lowerchambers 54 a, 54 b. According to embodiments of the present invention,and as described in great detail below, with the thermal gradientranging from about 1° C. to 130° C., preferably from about 25° C. toabout 80° C., and more preferably from about 40° C. to 60° C.

The heaters 72, 74 may have any suitable structure, form, or number.Particularly, and as shown, band heaters 72, 74 are used tocircumferentially surround the 58 and chamber 54 therein. Otherconstructions and methods may be used, so long as a temperaturedifference exists along a longitudinal axis 77 of the chamber 54 of theautoclave 56.

Referring again to FIG. 1, with reference to FIG. 2A, and with thefeedstock and mineralizer solution (collectively illustrated as liquid57) prepared within the chamber 54, a seed crystal 80 may then besuspended within the upper chamber 54 a (Block 78). The crystalsuspension 82 may include wires, clamps, and woven wire mesh constructedfrom an inert material, such as a precious metal.

If necessary, although not shown, de-ionized water may be added to thechamber 54 such that a total volume of solution 57 and water occupiesabout 40% to about 95% of the chamber's internal volume.

Continuing with FIGS. 1 and 2, the chamber 54 of the autoclave 56 maythen be sealed, pressurized (for example, at a pressure of from about200 psi to about 100,000 psi, preferably from about 10,000 psi to about40,000 psi, more preferably from about 20,000 psi to about 25,000 psi),and heated (Block 84). In Block 86, a temperature gradient is formedalong the longitudinal axis 77 of the chamber 54. In that the lowerchamber 54 b may be heated to a temperature range of from about 200° C.to 1000° C., preferably from about 300° C. to about 700° C., morepreferably from about 350° C. to 450° C. This high temperature causes apartial amount of the uranium nutrient/feedstock to enter themineralizer solution. Concurrently, the upper chamber 54 a may be heatedto a temperature range of from about 50° C. to 950° C., preferably fromabout 200° C. to about 600° C., more preferably from about 300° C. to400° C., but less than the temperature of the lower chamber 54 b. At thelower temperature, the solubility of nutrient in the mineralizersolution is reduced and, resultantly, nutrient will precipitate out ofsolution and spontaneously grow crystals onto the seed crystal 80 (FIG.2A). More generally, the maximum temperature may range from about 400°C. to about 750° C., with the thermal gradient ranging from about 1° C.to 130° C., preferably from about 25° C. to about 80° C., and morepreferably from about 40° C. to 60° C.

Heating and crystallization continue (“No” branch of decision block 88)until a final crystal is achieved and having one or more of a desiredpurity, a desired quality, and a desired size. While thesecharacteristics of the final crystal are at least partially dependent onreaction duration, generally crystal growth continues for about 7 daysto about 90 days.

When the desired growth is achieved (“Yes” branch of decision block 88),the process ends, the heat and pressure are removed from the chamber 54such that crystal may be retrieved.

According to some alternative embodiments, the thermal gradient need notbe applied nor maintained. Instead, crystal growth may be foundfavorable using an isothermal temperature.

According to some embodiments of the present invention, the use of oneor more seed crystal 80 may be required or desired. In that regard, andwith reference to FIG. 3, a baffle-based seed ladder 90 is shown. Thebaffle-based seed ladder 90 includes a baffle portion 92 and a ladderportion 94 and, thus, may comprise a unitary construction or,alternatively, may be separately constructed and joined together. As wasnoted above, the construction may include any inert material, forexample, precious metals.

The baffle portion 94 includes an opening 96 within a main body 98having a diameter, d₂, selected to permit fluid communication therethrough ranging from about 15% to about 45% and so as to permit fluidiccommunication between the upper and lower regions 54 a, 54 b (FIG. 2A)of the chamber 54 (FIG. 2A) while maintaining these regions 54 a, 54 b(FIG. 2A) as separate.

The ladder portion 94 includes a one or more rungs 100 (three rungs 100are shown) extending from vertical supports 102. Seed crystals 80 (twoseed crystals 80 are shown) are positioned between adjacent ones of therungs 100 by at least one suspension 82, which may be similar to thesuspensions discussed in detail above.

Use of the baffle-based seed ladder 90 may provide the benefit ofgrowing more than one crystal at a time in accordance with embodimentsof the present invention as described in detail here.

Turning now to FIGS. 4 and 5, a method of forming crystals according toanother embodiment of the present invention is shown. In Block 112, anampoule 114 configured to be positioned within a chamber 116 of apressurizable reaction device 118 is prepared with a feedstock and amineralizer solution. As described previously, the composition of thefeedstock and the mineralizer solution depends, in part, of the desiredcrystal yielded and may be selected in accordance with the parametersset forth above. Again, mineralizer solutions may have concentrationsranging from about 0.1 M to about 30 M.

The exemplary pressurizable reaction device 118 illustrated in FIG. 5 issimilar to the autoclave 56 of FIG. 2B; however, those skilled in theart having the benefit of the disclosure provided herein would readilyappreciate that the illustrated structure is non-limiting. Here, thedevice 118 includes a wall 120 enclosing the chamber 116. The chamber116 is accessible through an open end 122, into which a plug 124 andseal 126 may be inserted before pressurizing the chamber 116 and securedwith a locking collar 128.

Externally, heaters 130, 132 (two are shown), similar to those describedabove, at least partially surround the wall 120 of the device 118. Theheaters 130, 132 may be operably controlled by a controller 134 such atemperature gradient is created along a longitudinal axis 77 (FIG. 2A)of the chamber 116. According to embodiments of the present invention,and as described in great detail below, the temperature gradientvariation may range from about 1° C. to 130° C., preferably from about25° C. to about 80° C., and more preferably from about 40° C. to 60° C.

The ampoule 114 may be constructed of a precious metal (silver, gold,platinum, or palladium, for example) and, according to some embodimentsof the present invention, may comprise a metal tubing, such as thosecommercially-available from by Refining Systems, Inc. (Las Vegas, Nev.)and having one end welded or otherwise closed to retain the feedstockand the mineralizer solution therein.

Referring again to Block 112, the feedstock and the mineralizer solutionare added to the ampoule 114 until a combined total of the feedstock andmineralizer solution within the ampoule is set to occupy a majoritypercentage (ranging from about 40% to about 90%) of the ampoule's totalvolume. The ampoule 114 may then be sealed (for example, by welding anyopen end) and is positioned within the chamber 116 of the device 118 ofFIG. 5 (Block 136). If necessary, although not shown, de-ionized watermay be added to the chamber 116 such that a total volume of ampoule 114and water occupies about 65% to about 90% of the chamber's internalvolume.

Continuing with FIGS. 4 and 5, the chamber 116 of the device 118 maythen be sealed, pressurized (for example, at a pressure of from about200 psi to about 100,000 psi, preferably from about 10,000 psi to about40,000 psi, more preferably from about 20,000 psi to about 25,000 psi),and heated (Block 138). In Block 140, a temperature gradient is formedalong the longitudinal axis 77 (FIG. 2A) of the chamber 116, which maygenerally coincide with a longitudinal axis (not shown) of the ampoule114. In that regard, the ampoule 114 will have a lower region 114 aheated to a temperature that is greater than a temperature of an upperregion 114 b. It should be readily appreciated that the terms “lower”and “upper” are merely used as directional reference herein with respectto FIG. 5 and should not be considered to be limiting.

According to some embodiments, the highest temperature of the ampoule114 at the lower region 114 a will be a temperature range of from about50° C. to 950° C., preferably from about 200° C. to about 600° C., morepreferably from about 300° C. to 400° C., but greater than thetemperature of the lower chamber 114 b. At this high temperature,uranium nutrient/feedstock enters the mineralizer solution. The upperregion 114 b may then heated to a temperature range of from about 50° C.to 950° C., preferably from about 200° C. to about 600° C., morepreferably from about 300° C. to 400° C., but less than the temperatureof the lower chamber 114 a. At the lower temperature, the solubility ofnutrient in the mineralizer solution is reduced and, resultantly,nutrient will precipitate out of solution and spontaneously formspontaneously crystals on an inner wall (not shown) of the ampoule 114).

Heating and crystallization continue (“No” branch of decision block 142)until a desired growth is achieved. While the final size of the crystalis dependent on reaction duration, generally crystal growth continuesfor about for a period of from about 24 hours to about one year,preferably from about 14 days to about 180 days, more preferably fromabout 90 days to about 120 days.

When the desired growth is achieved (“Yes” branch of decision block142), a decision is made as to whether larger crystals are desired(Decision block 144). If larger crystals are desired (“Yes” branch ofdecision block 144), then heat and pressure are removed from the chamber116, the ampoule 114 opened, and a small crystal may be extracted fromthe inner wall of the ampoule 114 (Block 146). The small, extractedcrystal may then be used as a seed crystal in the method 50 (FIG. 1)described above. Otherwise (“No” branch of decision block 144), theprocess ends, the heat and pressure are removed from the chamber 116 andthe ampoule 114 opened such that crystals may be retrieved.

Similar to the alternate embodiment described above, an ampoule 150,used in accordance with methods described herein, may further comprise abaffle 152, with or without a seed ladder 154, the latter of which isshown in FIG. 6 (the ampoule 150 being in phantom). The baffle 152 withladder 154 may comprise a unitary construction of an inert material(such as a precious metal) or, alternatively, may be separatelyconstructed and joined together. As was noted above, the constructionmay include any inert material, for example, precious metals.

The baffle 152 includes an opening 156 within a main body 158 having adiameter selected to permit fluid communication there through rangingfrom about 15% to about 45% and so as to permit fluidic communicationbetween the upper and lower regions 150 b, 150 a of the ampoule 150while maintaining these regions 150 b, 150 a as separate.

The seed ladder 154 includes a one or more rungs 160 (three rungs 160are shown) extending from vertical supports 162. Seed crystals 80 (twoseed crystals 80 are shown) are positioned between adjacent ones of therungs 160 by at least one suspension 164, which may be similar to thesuspensions discussed in detail above. In this way, more than one seedcrystal 80 may be used for growing crystals.

Test Methods

Method of determining crystal structure. For purpose of thisspecification, a Rigaku XtaLab Mini is used to generate the data neededto determine crystal. The software used to collect the data andintegrate it is Crystal Clear Expert 2.0 r14. The final crystalstructure is solved using Shelxtl Version 6.10. The followingcoordinates are obtained via this method:

-   -   cell length a;    -   cell length b;    -   cell length c;    -   cell angle alpha;    -   cell mangle beta;    -   cell angle gamma and    -   x, y and z coordinates for U1, O1 and Na1.

EXAMPLES

The following examples illustrate particular properties and advantagesof some of the embodiments of the present invention. Furthermore, theseare examples of reduction to practice of the present invention andconfirmation that the principles described in the present invention aretherefore valid but should not be construed as in any way limiting thescope of the invention.

Example 1

Single crystal NaUO₃ by the hydrothermal technique. Utilizing twodistinct temperature regimes UO₃ feedstock is dissolved into amineralizing solution (NaOH), transported via convective flow to thecooler region. The cooler region, having a lower solubility limit thanthat of the hotter region, promotes precipitation of NaUO3. Theprecipitates can nucleate either spontaneously (SN) on the wall of theampule, or via transport growth on a seed crystal. Growth conditionsutilize a 1.25 inch internal diameter autoclave constructed from Inconel718. A sealed, 4 inch long by 0.25 inch internal diameter platinum tubewith the reactants is loaded into the autoclave and 90% fill counterpressure water is added to the autoclave to prevent the platinumcontainer from rupturing. The interior of the platinum tube has 0.040grams of powder UO₃ and 0.060 grams of ZnSe feedstock added to thebottom section of the tube. 0.4 mL of 6 M NaOH (sodium hydroxide) isadded to the tube prior to sealing (welding) it shut. The platinumreaction tube is then loaded into the autoclave. Two external bandheaters are affixed to the autoclave, allowing the controlled creationof a thermal gradient inside the autoclave. The bottom band heater isbrought to and held at 400° C. The upper band heater is brought to andheld at 350° C. The application of the conditions generates 15-20 kpsiof pressure. The conditions are maintained for 10 days before cooling toroom temperature.

Once the platinum tube is removed from the autoclave and opened, thecontents are collected on filter paper and the single crystals arecharacterized by single crystal X-ray diffraction, the results of whichwere determined to be the R32 NaUO₃ phase single crystals larger than370 microns, as characterized by single crystal X-ray diffraction.

Example 2

Single crystal NaUO₃ by the hydrothermal technique using a seed crystal.The process of Example 1 is repeated accept a portion of the NaUO₃produced in Example 1 is used as a seed crystal.

Example 3

Single crystal NaUO₃ by the hydrothermal technique using a non-nativeseed crystal. The process of Example 1 is repeated accept a non-nativeseed crystal. Suitable non-native seed crystals include MgTiO₃, BaTiO₃,and other perovskite structures.

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While the present invention has been illustrated by a description of oneor more embodiments thereof and while these embodiments have beendescribed in considerable detail, they are not intended to restrict orin any way limit the scope of the appended claims to such detail.Additional advantages and modifications will readily appear to thoseskilled in the art. The invention in its broader aspects is thereforenot limited to the specific details, representative apparatus andmethod, and illustrative examples shown and described. Accordingly,departures may be made from such details without departing from thescope of the general inventive concept.

What is claimed is:
 1. A single crystalline NaUO₃ having a R32 spacegroup.
 2. The single crystalline NaUO₃ of claim 1 said crystal has acrystal volume of at least 1.31×10⁻³ cubic millimeters.
 3. The singlecrystalline NaUO₃ of claim 1 having the following coordinates: a) a celllength a of 5.8700(8)Ã-; b) a cell length b of 5.8700(8)Ã-; and c) acell length c of 7.1180(14)Ã-.
 4. The single crystalline NaUO₃ of claim3 having the following, coordinates: a) a U1 having x=0.0000, y=0.0000and z=−0.0000; b) a O1 having x=0.231(14), y=0.3333 and z=0.21(5); andc) a Na1 having x=0.6667, y=0.3333 and z=2.031(4).
 5. A process making asingle crystalline NaUO₃ having a R32 symmetry structure, said processcomprising autoclaving for a period of from about 24 hours to about oneyear, at a pressure of from about 200 psi to about 100,000 psi, acontainer comprising an ampoule having a bottom feedstock zone and a topcrystal growth zone, said bottom feedstock zone having a temperaturerange of from about 200° C. to 1000° C., and top crystal growth zonehaving a temperature range of from about 50° C. to 950° C., said processhaving a temperature gradient between said bottom feedstock zone andsaid top crystal growth zone of from about 1° C. to 130° C.; saidcontainer comprising: 0.001-4.999:5 internal fill to ampoule volume,0.01-8:4 feed stock to mineralizer, from 0.01:4 to 4:0.01 of eachpowdered feed stock.
 6. The process of claim 5 comprising autoclavingfor a period of from about 14 days to about 180 days, at a pressure offrom about 10,000 psi to about 40,000 psi, a container comprising anampoule having a bottom feedstock zone and a top crystal growth zone,said bottom feedstock zone having a temperature range of from about 300°C. to about 700° C., and top crystal growth zone having a temperaturerange of from about 200° C. to about 600° C., said process having atemperature gradient between said bottom feedstock zone and said topcrystal growth zone of from about 25° C. to about 80° C.; said containercomprising: 2-4.5:5 internal fill to ampoule volume, 0.5-3:4 feed stockto mineralizer, from 1:4 to 4:1 of each powdered feed stock.
 7. Theprocess of claim 6 comprising, autoclaving for a period of from about 90days to about 120 days, at a pressure of from about 20,000 psi to about25,000 psi, a container comprising an ampoule having a bottom feedstockzone and a top crystal growth zone, said bottom feedstock zone having atemperature range of from about 350° C. to 450° C. and top crystalgrowth zone having a temperature range of from about 300° C. to 400° C.,said process having a temperature gradient between said bottom feedstockzone and said top crystal growth zone of from about 40° C. to 60° C.;said container comprising: 4:5 internal fill to ampoule volume, 1:4 feedstock to mineralizer, 1:1 of each powdered feed stock.
 8. The process ofclaim 7 comprising, said process having a temperature gradient betweensaid bottom feedstock zone and said top crystal growth zone of about 50°C.
 9. The process of claim 5 wherein said crystal growth zone of saidcontainer comprises a seed crystal, preferably said seed crystal has aPm-3m space group.
 10. The process of claim 9 wherein said seed crystalhas: a) a cell length a of 5.8700(8); b) a cell length b of 5.8700(8);c) a cell length c of 7.1180(14); d) a cell angle alpha of 90.00; e) acell mangle beta of 90.00; and f) a cell angle gamma of 120.00.
 11. Theprocess of claim 10 wherein said seed crystal has: a) a U1 havingx=0.0000, y=0.0000 and z=−0.0000; b) a O1 having x=0.231(14), y=0.3333and z=0.21(5); and c) a Na1 having x=0.6667, y=0.3333 and z=2.031(4).